Hydroxyacetylated drastically-oxidized ricinoleic acid compounds and method of making same



Patented Aug. 2Q, 1946 -HYDROXYACETYLATED DRASTICALLY-OX- ,IDIZED' RICINOLEIC ACID COMPOUNDS AND METHOD or MAKING SAME Melvin,De Groote, University City, Bernhard Keiser, Webster Groves, and Arthur F. Wirtel, Kirkwood, M0., assignors to Petrolite Corporaj tion, Ltd.,,VVilmington, DelL, a. corporationlof- N Drawing Application July6,-1943,

= Serial'No.493,684

flhis invention, relates to a new'composition of matter, our present -application being a continu- .ation-in-part of our pending application Serial No. 444,468, filed May 25, 1942, which subsequently matured as U. S. Patent No. 2,340,308, dated February 1, 1944, I

Qneobject, of our invention is to provide a new chemical product that is particularly adapted for use as a demulsifier in the resolution of crude oil-emulsions. l v

.Another object of our invention is to provide new chemical product. or compound.

Although one of the primary objects of our invention is to provide -a new compound or composition of matter that is an efficient demulsifier for crudeloil emulsionsof the. water-in-oil type, the 'said compound or composition of matter is adapted for use in other arts, as hereinafter ina. practicable method for manufacturing said icated. It may also haveadditional uses in other fields which have not yet been investigated. z 1 j I he composition of matter; herein described, particularly when it is intended 'to "be used as a demulsifier forpetroleum' emulsions "oi the W9;- ter-in-oil type, may be obtained by the 'hydroxyacetylation of-blown or oxidized ricinoleic acid compounds, or compounds of the kind hereinafter-described. Morespecifically, the composition of matter herein contemplatedxand pa-rticularly for use as a demulsifier, is obtained by treating oxidized ricinoleic acidcompounds with a concentrated solution of hydroxyacetic acid, or

.cciaims. 01. 260-5406) 2 I I 1 leate, cobalt ricinoleate, manganese ricinoleate, etc;, it may be of the organic type which produces peroxide such as alpha-pinene, linseed oil, etc. Oxidation may take-place at atmospheric pressure or superatmospheric pressure, i. .e., jpressuresvup to or including .200 pounds perfs'qliare inch gauge pressure, and at anyv temperature,

slightly above the boiling pointlof'water, for instance, 120 C., up to any temperature which does not produce undue decomposition by ,pyrolytic reaction. 'Ifhe time of blowing may be fairly brief, for example, 8-10 hours; or it may be quite extensive, for instance as long as 10-12-14 days, the longer time periods-being employed generally when the temperature is just slightly abovethe boilingpoint of water and when'ioxidation is with air at atmospheric pressure. a I

Mild oxidation, 1. e., oxidation as exemplified bythe exposure of a filinof castor oil to air, for an extended period of time, such' as weeks,,or even months, (see Chemical Technology and Analysis of Oils, Fats,---and Waxes, byLewkowitsch, sixth edition,- volume 2, -page-=406)' produces" relatively-small modifications of certain important iiidices, such as the iodinevalua'the acetyl'value, and the saponification value. *If drastic oxidation takes place, either bycontinued mild oxidation, -or-by-more vigorousroxidatiozi' anhydrous hydroxyac'etic'acid'in the ratio of at least two moles of thehydroxyacetic acidand not more thanS moles of the hydroxyacetic acid for each ricinoleyl: radical present-prior to drastic; oxidation.- That is to say, if one were to; start with a pound mole of oxidized triricinoleim one would employ at least six :poundmoles and, not more thannine -pound moles of;-jhydr0Xyacetic acid.

i It is well known that oxidized oils can be obtained from castor oil, ricinoleio acid and various derivatives of ricinoleic-acid, such as:' Monoric inolein, -diricin olein and polyricinoleic acids. They are producedby the common practice of blowing or oxidizing castor oil and similar fatty oils or acids, particularly non-drying unsaturated fatty:oils,- by ;me ans of agaseous medium; such as-air, oxygen, ozone, or'ozonized-air. The gaseous medium,,such,as air, may, be moist or m and t ox a i n, ma i ke'lp e e n Et presence or absence, of; a-catalyst.- ,fIfhe catalyst may be of a metallic type, such aslead ricinofrom the very beginning of the reaction; asinduced by-either a higher reaction-temperaturelor the presenceof a catalyst, then there is obtained an oxidized .oil having-l; characteristics which clearly-indicate that drastic oxidation has taken place; These indic eslot. drastic oxidation fare ia relatively low iodinevalue, such as '70 or less, and may be as low as 40, or thereaboutsjfla'saponification value of 215 to 283,.or thereabouts; an acetyl value oflapproximately 160-200; anincreased viscosity such that the material may be hardly mobile at ordinary temperatures; a specific gravity of almost one, or a trifle over oneat times; an increased refractive index; and,.in' the absence of other coloring matter, a yellow'to deep orange color. The color at times may be a questionable index, since some oxidized -castor oils are bleached to make, them particularly adaptable for useas plasticizers in light colored resinoid bodies.

Drastically-oxidized castor oil can-be prepared bywell-known methods, or such products canbe purchased in the.,op'en market under 1 various trade names, 'suchas blownicastor oil, blend-..

essed castor oil,loxidiz ed castor -'oi1,""havy castor oil, viscous castor oil," etc. These various trade names appear to be applied to drasti- (sally-oxidized castor oils, which difier merely in j degree but not; kind.

The color; of these-oils is stilf pal'e .orfli ght colored in comparison with the oil from which For the sake of difierentiation, oilsdfthe kind previously described will be referredto as pale i blown, drastically-oxidized castor oils; and the same terminology is intended to apply to all, other ricinoleic bodies of the kind hereinafterd'e derived, both from the water vapor and solvent vapor, is separated by gravity; and the solvent returned to the reacting chamber for further use.

The selection of suitable amounts of reactants in the manufacture of hydroxyacetylated blown castor oil is, of course, simple. ,may be analyzed so as to determine its hydroxyl orv acetyl value. Such value may be interpreted onzther basis of each fatty acid radical present. The acetyl value or hydroxyl value may not correspond exactly to the alcoholic hydroxyl radicals attached to each high molal fatty acid acyl radicalibut suchvalue does correspond, at least, approximately. The reason is that there may be present anhydrides, or possibly, some compounds of unknown nature or stability, which affect the hydroxyl. value determination. For convenience ins-the present instance, one may consider blown triricinolein in the same manner that it is'scmetimes convenient to consider triricinolein, i. e.,

as if it were a trihydric alcohol. For practical td-S'tebr'," dated December'lcl 19 35. The product described'in said Stehr patent is characterized by the fact that drastic oxi'dation is continued past whereas a matter of fact, a-superoindized prodthe stage where a pale blown oil is obtained and deter almostsemi-livery consistenc is obtained.

Such prod cts are-usuall much d'ark'er in color 'than-thepale blown castor oils, for the reason tliat'ceftain sidereac'tionsoccur with-the formaiiatur'e. r v I Attention is directed particularly to U. S. Pattion of dark ooIored-byroducts; and asa're'sult, the transparency of the oil has greatly decreased or disappeared, and it is apt to be opaque in cut 2,183,487, dated December 12, 1939, to'

Colbetli, to theextent that it discloses details as to the oxidation of castoroil'ina mannerthat is particularly desirable;

A Our preferenceis to subject a pale'blo'wn castor oil of the following characteristics,to hy- The production r hydroxyacetylated 'bl'own castor oil or similar compounds, "is comparatively 'simpleandis comparable to the manufacture of acetylated castor .oil, except thathydroxyacetic acid'crits' equivalent,such as the anhydri-de or am chloride, is employed; and castor oil is 'replaced by 'theblown product. In View of, the acetyl or hydroxyl value of blown castor oil, the principal reaction is obviously an esteriflcation reaction in which the 'reaction is hastened or formed, :forinstance, 120-18 (3.; sometimes the presencecf .a strong "acid, "such as a benzenesu'lfon'ic acid in'sm'all'amountsacts as a'catalyst; sometimesit is expedient to pass-an inert'dried gasthrough the reaction mixture; at other times esterification may "be conductedin the presence i ofahighiboiling water-insoluble"solvenusuch .as xylene or the like, which assists in'removing the water in; th f im jv n r h ensate so purposes; of course, there is no economical justi fic'ation for obtaining-a technicallyv pure blown triricinolein and subjecting such material to hydroxyacetyl-ation instead of employing blown castor'oil.

Thus, the product constituting our present inventien isthe compound or compounds obtained which-represent, in essence, a polyhydroxyacetic acid derivative of blown castor oil. The 'unhyphenated expression polyhydroxyacetic acid is employed to reform polymeric derivatives of hydroxyacetic acid in the same way that polyricinoleic acid refers to polymeric derivatives of ricinol'ei'c acid. Suchacid's are obviously ester acids produced by self-'esterificati'on. p

The constitution of such polyhydroxyacetic acids and their relationship to hydroxyacetic acid is readily shown'by the following formulas:

In the presentinstance; however, the polyhydroxya'cetic acids, in "View ofthe previous limitation, are" concerned onlyw'ith the species in which the formula takes either one or the other of two forms; Y

- QH CH2COO 2H OH(CI -I2COO).3H

What has been said previously may suggest an oversimplificat-ion of a rather complicated structure, which resultsfrom the reaction or re- 7 actions indicated. For instanca'theexamination of 'the'reaction between'hydroxyacetic acid and castor oil, orhydroxyacetic acid and blown castor The blown oil monoglycerides and 'diglycerides .are present. Specific terminology indicated inthe present instance would be :superglycerinated' blown caster oil. Likewise,-the acids and polymerized acids obtained from the blown :caston oil,iare"so'metimes reierred'to as a blown castoroil'estolide.

(See U. S. Patent No. 2,079,762, dated May 11, 1937, to De Grooteand Keiser.) In addition to "the other products formedlby hydrolysis, glycerol must be included.= It is not intended in the present instance toclaim the product obtained by hydroxyacetylation of glycerol, but it" is .to be noted that such material may be present cogenerically, for reasons indicated. Earlier ref- 'erences to the compounds herein contemplated, and particularly for use as a demulsifier, include 'quently. The preferred example isthe cogeneric mixture obtained bythe polyhy'droxyacetylation of blown castor-"oiL- One may employ superlycerina'ted blown castor oil obtained by reaction between blown castor oil and g'lycerine, in the 'pr'oportionof one o'r jtwo moles of. glycerolpjer mole ofblown castor 'oil. This simply means that the product is obtained by rearrangement instead of hydrolysis. bvi'ously, one may also employ technically pure blown mon'oricinolein, technically pure blown diricin'olein, and technically u e blown ricinolei'c acid. V i I r Although it is believed,'in view 0t what has been said, that no' further description is necessary in regard to the manufacture of hydroxyacetylated blown ricino'leicacid compounds, the following examples are included by way of illustration:

HYnaoxYAcarYmrsp, Brown CASTOR 011.

Example 1 1,000 pounds of pale blown castor oil corresponding to the tabular specifications above is treated with 666 pounds of concentrated hydroxyacetic acid containing of water. tion is conducted at 200-250" C. for approximately 2% to 4 hours. Completeness of reaction is indicated by the fact, that elimination of water practically ceases by decrease in the acid value and hydroxyl value of the mixture, and by elimination of free hydroxyacetic acid. The Procedure is conducted in the usual reaction vessel of the kind employed for esterification, and may be constructed of any material which is resistant to the reactants. The amount of hydroxyacetic acid selected in the present instance is calculated to give substantially the equivalent of a mole of an OH(CH2COO)2H radical for each ricinoleyl radical originally present.

HYDROXYACE'IYLATED, BLOWN CASTOR Q11.

Example 2 The sam procedure is followed as in Example 1, preceding, except that more of hydroxyacetic acid is used, i. e., approximately 1,000 pounds of hydroxyacetic acid, or sufficient .for the presence of an OI-I(CH2COO):H radical for each ricinoleyl radical originally present.

The reac- HYnnoxYecnmArEmBLown GASTOR 0n. '3'

' Example 3 v Thesame procedure is employed asin the-two pre ed ng examples, e pt hat 83. r unds o hydroxyacetic acid are employed, i..e .an amount .which would result theoretically in av mixture of the dimeric and trimeric radicals. 1 Q Hirimoxim'cniryns'r ni, BLOWN CASTOR'QIL Y Example 4 x I The same procedure is followed as in Examples 1. to 3, precedingjexcept that anhydrous hydroxyiacetic'acid is employed and water is removed immediately upon "formation. The productfso '"obtained represents polyhydro'xyacetylated blown castor oil, orimore especially, polyhydroxyacet- :ylated' blown vtriricinc'ile'in, in the presence-of a minimum amount of .polyhydroxyacetylated "coeners T It is well known that the exact composition-of. ordinary oxidized castor oil "is not known. This 'hasbeen a matter of commentfrom time to" time in the? literature, including thepatent literature dealing-with the arts in which blownjcastor oil is contemplated. In view of -such fa'cts,it becomes even' more' difficult to 'attempt' to" indicate the nature of the products obtained by hydroxyacetylation of blown castor oil-or-the like; 'As has been previously indicated; esterificationgand quite frequently, hydrolysis, enters into the reaction, and it is quite probable, especially when aqueous hydroxyacetic acid is employed, thatrear- 'rangemennas exemplified by the formation'pf .estolidesj m'ay take place: The polyhydroxya'cetylated de'rivatives h'erein contemplated as new compositions of matter; and particularly for-'use as demulsifiers, maybe 'obtained in any suitable manner. Hydroxyacetyl- :ated blowin castor' oil prepared in anyisu'itable 'mannerr-may be reacted further with an additional amount of hydroxyacetic acid. Another way of saying the same thing, is that in preceding Example 1, if desired, the pale blown caspossibilities.

tor oil might have been reacted with 333 pounds of concentrated hydroxyacetic acid, and upon completion of the reaction, it could have been subjected to further reaction with another 333 pound lot of the reactant.

Furthermore, hydroxyacetic acid, that is, the monomeric acid, might be converted into the dimer or trimer, and such dimerlc or trimeric acid be employed as a reactant. Then too, one might employ the obvious functional equivalent of hydroxyacetic acid, such as the acyl chloride or the anhydride. In other words, although we have described the preferred method of manufacturing the new compositions of matter herein contemplated, and particularly for use as demulsifiers, it is understood that any feasible procedure may be used.

At this point it may be well to restate some of the data previously presented in regard to thecompositions contemplated. The expression polyhydroxyacetylated must be employed with a certain amount of caution, in view of certain For instance, if one pound mole of blown castor oil were reacted with 6 pound moles of strong hydroxyacetic acid in the manner previously described, it is within the realm of possibility that all the hydroxylacetic acid radicals might ultimately be combined into the monomeric form. The hydrolysis of the blown castor oil would result in the formation of glycerol, and one pound mole of glycerol could com- The other 3 pound molesot hydroxyacetic acid. couldthen combine with the 3 pound moles of *biow'n acids; termed" hydrolysis orj saponifidirevious" reference-has :made: to certain specificihydroxyacetylated derivatives of blown micinoleic, acid -componnds-. These additional I members include bl'ovizn d-iiiicinoleimblownnriorm ricinoleina:supergzlycerinated blown .oastor oil,

ib- 3;, .castor oi}v whic'l'i has been blown and then lsup r lycerinated; as diiierentiate'di from: one which; is supecglycerinated and .themblown, and also blown ricinoleic acid and blown polyricinoleio -azcid. 'l

iT-he,--:-herein rdeseribed chemical: compounds: or

3 pnoductsa neroi distinctrvalue ass a -break inducer in. the doctor treatment of gasoline or the like, as described. S-. Patent No. 2,157,223, to Other additional uses include. application::asjplasticizera, in: plas- .t;i c s;', synthetic .resins;, etc., and particularly in the acetate type; 15e,, the" cellu-loseacetate; vinyl Having thus: deseribed our inventiomrwhat we claim as' -new anddesire-to secure by Patentds': p v

1, Anew composition, consisting of V a: hydroxy acetylated drastically-oxidized ricinoleic a a'cid compound selected from. the" class? consisting of blown fcastoroil, blown 'triricin'olein, blown diri cinoleimLblown: monoricinoiein blown superglycanimated, castor oil, :superglycerinatedz blown leastorr 01 1-,- blown ricinoleic acid; blownipolyniclnoleic acid,-,. and blown oaster oil estolides; the iratiowof binei fiitli tnieemolesai iii droxyacetic acid.

' in oncmeiiic;'hydrbxyactiacidatoriiicinoleiczaciil :;radicals zpresentzpi'iornto di astio oxfdationi being airlea'st 21 to- 1 andnot'moi'e than 3213021;

- 2. A- new compositional-consisting of: a2 hydroxiacetylated' rdrasticallyeoxidized caster oilce-Hthe ratio ofxmonoineric hydroxyacetic acidtm ricinioleicsacid radicalsipnesent iprior itovdrasfie oxida tiom "being at least t'ol and not more-than: 3 tola v 3. Anew composition, con-sisti-ngfofiasihydmxyacetylated ,drasticallyroxidizedz :c'astor' oil; the

7 ratio 01: monomeric hydroxyaceticacidmadicals to ricinoleic acid radicals present prion to: drastic oxidation being 2*to 1-. .1 f

4. Anew composition; aeonsistingnofia m dwayacetylated drastically oxidi-zed caster; 4iil -the ratioofmonomeric hydroxyacetic :acid radicals to ricinoleic; acidradicalspresent-prior: to disastic oxidationbeingrz toil; v V

news-composition, consistingrota hyd-isoxyacetylated; drastically-oxidized; caster -:oi-l the ratio of monomeric hydromacetic acid radicals to'ricinoleic acid: radicals :present prior ,to-drastic oxidation being 3 to! ill I r 16.. Inicthe manufacture ofthe compoundbde- V scribed in-cIa-im1 1,. the steps-oi (a) drasticallyoxidizing: :a =ricino1eic1 acid: compoundselected f-rom: theclass consisting of: blown castoit :oil, blown triricinolein-,:b1own .diricinol-ein, blown monoricinolein; blown staperglycerinateck castor' oil, superglyceninated blow-n castoac{ oil blown 'rici'noleic acid, blow-n. polyi i-cinoleic acid; and blown caster oilestolides; and: b) .hyd-roxyacetylating said: aforementioned:drastically-oxidized 'ricinoleic acid compound; thearatioof: monomeric hydroxyacetic acid towricinoleic-acidmadk cals vpresent prior to'drastic ioxidation being: at -1east2-to::1and netmorflthandizo 1'. 

